Structural approach to charge density waves in low-dimensional systems: electronic instability and chemical bonding.

The charge density wave (CDW) instability, usually occurring in low-dimensional metals, has been a topic of interest for longtime. However, some very fundamental aspects of the mechanism remain unclear. Recently, a plethora of new CDW materials, a substantial fraction of which is two-dimensional or even three-dimensional, has been prepared and characterised as bulk and/or single-layers. As a result, the need for revisiting the primary mechanism of the instability, based on the electron-hole instability established more than 50 years ago for quasi-one-dimensional (quasi-1D) conductors, has clearly emerged. In this work, we consider a large number of CDW materials to revisit the main concepts used in understanding the CDW instability, and emphasise the key role of the momentum dependent electron-phonon coupling in linking electronic and structural degrees of freedom. We argue that for quasi-1D systems, earlier weak coupling theories work appropriately and the energy gain due to the CDW and the concomitant periodic lattice distortion (PLD) remains primarily due to a Fermi surface nesting mechanism. However, for materials with higher dimensionality, intermediate and strong coupling regimes are generally at work and the modification of the chemical bonding network by the PLD is at the heart of the instability. We emphasise the need for a microscopic approach blending condensed matter physics concepts and state-of-the-art first-principles calculations with quite fundamental chemical bonding ideas in understanding the CDW phenomenon in these materials.

Metastable Polymorphic Phases in Monolayer TaTe2.

Polymorphic phases and collective phenomena-such as charge density waves (CDWs)-in transition metal dichalcogenides (TMDs) dictate the physical and electronic properties of the material. Most TMDs naturally occur in a single given phase, but the fine-tuning of growth conditions via methods such as molecular beam epitaxy (MBE) allows to unlock otherwise inaccessible polymorphic structures. Exploring and understanding the morphological and electronic properties of new phases of TMDs is an essential step to enable their exploitation in technological applications. Here, scanning tunneling microscopy (STM) is used to map MBE-grown monolayer (ML) TaTe2 . This work reports the first observation of the 1H polymorphic phase, coexisting with the 1T, and demonstrates that their relative coverage can be controlled by adjusting synthesis parameters. Several superperiodic structures, compatible with CDWs, are observed to coexist on the 1T phase. Finally, this work provides theoretical insight on the delicate balance between Te…Te and Ta-Ta interactions that dictates the stability of the different phases. The findings demonstrate that TaTe2 is an ideal platform to investigate competing interactions, and indicate that accurate tuning of growth conditions is key to accessing metastable states in TMDs.

Bis(Vinylenedithio)-Tetrathiafulvalene-Based Coordination Networks.

Novel coordination polymers embedding electroactive moieties present a high interest in the development of porous conducting materials. While tetrathiafulvalene (TTF) based metal-organic frameworks were reported to yield through-space conducting frameworks, the use of S-enriched scaffolds remains elusive in this field. Herein is reported the employment of bis(vinylenedithio)-tetrathiafulvalene (BVDT-TTF) functionalized with pyridine coordinating moieties in coordination polymers. Its combination with various transition metals yielded four isostructural networks, whose conductivity increased upon chemical oxidation with iodine. The oxidation was confirmed in a single-crystal to single-crystal X-ray diffraction experiment for the Cd(II) coordination polymer. Raman spectroscopy measurements and DFT calculations confirmed the oxidation state of the bulk materials, and band structure calculations assessed the ground state as an electronically localized antiferromagnetic state, while the conduction occurs in a 2D manner. These results are shedding light to comprehend how to improve through-space conductivity thanks to sulfur enriched ligands.

Mixed-Valence Conductors from Ni Bis(diselenolene) Complexes with a Thiazoline Backbone.

Highly conducting, mixed-valence, multi-component nickel bis(diselenolene) salts were obtained by electrocrystallization of the monoanionic species [Ni(Me-thiazds)2]-1 (Me-thiazds: N-methyl-1,3-thiazoline-2-thione-4,5-diselenolate), with 1:2 and 1:3 stoichiometries depending of the counter ion used (Et4N+ and nBu4N+ vs Ph4P+, respectively). This behavior strongly differs from that of the corresponding monoanionic dithiolene complexes whose oxidation afforded the single component neutral species. This provides additional rare examples of mixed-valence conducting salts of nickel diselenolene complexes, only known in two examples with the dsit (1,3-dithiole-2-thione-4,5-diselenolate) and dsise (1,3-dithiole-2-selone-4,5-diselenolate) ligands. The mixed-valence salts form highly dimerized or trimerized bi- and trimetallic units, rarely seen with such nickel complexes. Transport measurements under a high pressure (up to 10 GPa) and band structure calculations confirm the semiconducting character of [Ph4P][Ni(Me-thiazds)2]3 and the quasi metallic character of [Et4N][Ni(Me-thiazds)2]2 and [NBu4]x[Ni(Me-thiazds)2]2 salts (0 < x < 1).

Intermolecular Resonance Correlates Electron Pairs Down a Supermolecular Chain: Antiferromagnetism in K-Doped p-Terphenyl.

Recent interest in potassium-doped p-terphenyl has been fueled by reports of superconductivity at Tc values surprisingly high for organic compounds. Despite these interesting properties, studies of the structure-function relationships within these materials have been scarce. Here, we isolate a phase-pure crystal of potassium-doped p-terphenyl: [K(222)]2[p-terphenyl3]. Emerging antiferromagnetism in the anisotropic structure is studied in depth by magnetometry and electron spin resonance. Combining these experimental results with density functional theory calculations, we describe the antiferromagnetic coupling in this system that occurs in all 3 crystallographic directions. The strongest coupling was found along the ends of the terphenyls, where the additional electron on neighboring p-terphenyls antiferromagnetically couple. This delocalized bonding interaction is reminiscent of the doubly degenerate resonance structure depiction of polyacetylene. These findings hint toward magnetic fluctuation-induced superconductivity in potassium-doped p-terphenyl, which has a close analogy with high Tc cuprate superconductors. The new approach described here is very versatile as shown by the preparation of two additional salts through systematic changing of the building blocks.

Ab initio studies of the optoelectronic structure of undoped and doped silicon nanocrystals and nanowires: the role of size, passivation, symmetry and phase.

Silicon nanocrystals and nanowires have been extensively studied because of their novel properties and their applications in electronic, optoelectronic, photovoltaic, thermoelectric and biological devices. Here we discuss results from ab initio calculations for undoped and doped Si nanocrystals and nanowires, showing how theory can aid and improve comprehension of the structural, electronic and optical properties of these systems.

Preferential Positioning, Stability, and Segregation of Dopants in Hexagonal Si Nanowires.

We studied the physics of common p- and n-type dopants in hexagonal-diamond Si, a Si polymorph that can be synthesized in nanowire geometry without the need of extreme pressure conditions, by means of first-principles electronic structure calculations and compared our results with those for the well-known case of cubic-diamond nanowires. We showed that (i) as observed in recent experiments, at larger diameters (beyond the quantum confinement regime) p-type dopants prefer the hexagonal-diamond phase with respect to the cubic one as a consequence of the stronger degree of three-fold coordination of the former, while n-type dopants are at a first approximation indifferent to the polytype of the host lattice; (ii) in ultrathin nanowires, because of the lower symmetry with respect to bulk systems and the greater freedom of structural relaxation, the order is reversed and both types of dopant slightly favor substitution at cubic lattice sites; (iii) the difference in formation energies leads, particularly in thicker nanowires, to larger concentration differences in different polytypes, which can be relevant for cubic-hexagonal homojunctions; (iv) ultrasmall diameters exhibit, regardless of the crystal phase, a pronounced surface segregation tendency for p-type dopants. Overall these findings shed light on the role of crystal phase in the doping mechanism at the nanoscale and could have a great potential in view of the recent experimental works on group IV nanowires polytypes.

Coexistence of Elastic Modulations in the Charge Density Wave State of 2 H-NbSe2.

Bulk and single-layer 2 H-NbSe2 exhibit identical charge density wave order (CDW) with a quasi-commensurate 3 × 3 superlattice periodicity. Here we combine scanning tunnelling microscopy (STM) imaging at T = 1 K of 2 H-NbSe2 with first-principles density functional theory (DFT) calculations to investigate the structural atomic rearrangement of this CDW phase. Our calculations for single-layers reveal that six different atomic structures are compatible with the 3 × 3 CDW distortion, although all of them lie on a very narrow energy range of at most 3 meV per formula unit, suggesting the coexistence of such structures. Our atomically resolved STM images of bulk 2 H-NbSe2 unambiguously confirm this by identifying two of these structures. Remarkably, these structures differ from the X-ray crystal structure reported for the bulk 3 × 3 CDW which in fact is also one of the six DFT structures located for the single-layer. Our calculations also show that due to the minute energy difference between the different phases, the ground state of the 3 × 3 CDW could be extremely sensitive to doping, external strain or internal pressure within the crystal. The presence of multiphase CDW order in 2 H-NbSe2 may provide further understanding of its low temperature state and the competition between different instabilities.

Engineering Polar Oxynitrides: Hexagonal Perovskite BaWON2.

Non-centrosymmetric polar compounds have important technological properties. Reported perovskite oxynitrides show centrosymmetric structures, and for some of them high permittivities have been observed and ascribed to local dipoles induced by partial order of nitride and oxide. Reported here is the first hexagonal perovskite oxynitride BaWON2 , which shows a polar 6H polytype. Synchrotron X-ray and neutron powder diffraction, and annular bright-field in scanning transmission electron microscopy indicate that it crystalizes in the non-centrosymmetric space group P63 mc, with a total order of nitride and oxide at two distinct coordination environments in cubic and hexagonal packed BaX3 layers. A synergetic second-order Jahn-Teller effect, supported by first principle calculations, anion order, and electrostatic repulsions between W6+ cations, induce large distortions at two inequivalent face-sharing octahedra that lead to long-range ordered dipoles and spontaneous polarization along the c axis. The new oxynitride is a semiconductor with a band gap of 1.1 eV and a large permittivity.

Charge Delocalization, Oxidation States, and Silver Mobility in the Mixed Silver-Copper Oxide AgCuO2 ¤.

The electronic structure of AgCuO2, and more specifically the possible charge delocalization and its implications for the transport properties, has been the object of debate. Here the problem is faced by means of first-principles density functional theory calculations of the electron and phonon band structures as well as molecular dynamics simulations for different temperatures. It is found that both Cu and Ag exhibit noninteger oxidation states, in agreement with previous spectroscopic studies. The robust CuO2 chains impose a relatively short contact distance to the silver atoms, which are forced to partially use their d z2 orbitals to build a band. This band is partially emptied through overlap with a band of the CuO2 chain, which should be empty if copper were in a Cu3+ oxidation state. In that way, although structural correlations could roughly be consistent with an Ag+Cu3+O2 formulation, the appropriate oxidation states for the silver and copper atoms become Ag(1+δ)+ and Cu(3-δ)+, and as a consequence, the stoichiometric material should be metallic. The study of the electronic structure suggests that Ag atoms form relatively stable chains that can easily slide despite the linear coordination with oxygen atoms of the CuO2 chains. Phonon dispersion calculations and molecular dynamics simulations confirm the stability of the structure although pointing out that sliding of the silver chains is an easy motion that does not lead to substantial modifications of the electronic structure around the Fermi level and, thus, should not alter the good conductivity of the system. However, this sliding of the silver atoms from the equilibrium position explains the observed large thermal factors.

2D Molecular Superconductor to Insulator Transition in the ß''-(BEDT-TTF)2[(H2O)(NH4)2M(C2O4)3]·18-crown-6 Series (M = Rh, Cr, Ru, Ir).

The series of salts ß''-(BEDT-TTF)2[(H2O)(NH4)2M(C2O4)3]·18-crown-6 show ambient-pressure superconductivity when M = Cr, Rh. Evidence indicates that the previously reported Cr and Rh salts show a bulk Berezinski-Kosterlitz-Thouless superconducting transition. The isostructural ruthenium and iridium salts are reported here. The Ir salt represents the first radical-cation salt to contain a 5d tris(oxalato)metalate anion. The Ru and Ir salts do not show superconductivity but instead undergo a broad chemically induced metal to insulator transition at 155 K for ruthenium and at 100 K for iridium. The c axes of the Ru and Ir salts are much shorter than those of the Rh and Cr salts. Thus, the more stable metallic state of the Cr and Rh salts is associated with the more strongly 2D electronic systems. The different low-temperature behavior of the Ru and Ir salts, which exhibit a smaller interlayer spacing, could originate from a structural change in the anionic layer which thus can be easily transmitted to the donor layers and generate a localized state. However, another possibility is that it originates from Berezinski-Kosterlitz-Thouless effects.

Magnetic Molecular Conductors Based on Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and the Tris(chlorocyananilato)ferrate(III) Complex.

Electrocrystallization of the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) organic donor in the presence of the [Fe(ClCNAn)3]3- tris(chlorocyananilato)ferrate(III) paramagnetic anion in different stoichiometric ratios and solvent mixtures afforded two different hybrid systems formulated as [BEDT-TTF]4[Fe(ClCNAn)3]·3H2O (1) and [BEDT-TTF]5[Fe(ClCNAn)3]2·2CH3CN (2) (An = anilato). Compounds 1 and 2 present unusual structures without the typical segregated organic and inorganic layers, where layers of 1 are formed by Λ and Δ enantiomers of the anionic paramagnetic complex together with mixed-valence BEDT-TTF tetramers, while layers of 2 are formed by Λ and Δ enantiomers of the paramagnetic complex together with dicationic BEDT-TTF dimers and monomers. Compounds 1 and 2 show semiconducting behaviors with room-temperature conductivities of ca. 6 × 10-3 S cm-1 (ambient pressure) and 1 × 10-3 S cm-1 (under applied pressure of 12.1 GPa), respectively, due to strong dimerization between the donors. Magnetic measurements performed on compound 1 indicate weak antiferromagnetic coupling between high-spin FeIII (SFe = 5/2) and mixed-valence radical cation diyads (BEDT-TTF)2+ (Srad = 1/2) mediated by the anilate ligands, together with an important Pauli paramagnetism typical for conducting systems.

Electronic engineering of a tetrathiafulvalene charge-transfer salt via reduced symmetry induced by combined substituents.

A 1 : 1 metallic charge-transfer salt is obtained by cosublimation of (Z,E)-(SMe)2Me2TTF and TCNQ. X-ray diffraction studies confirm the formation of segregated stacks comprising donor and acceptor molecules in [(E)-(SMe)2Me2TTF](TCNQ). The crystal packing features lateral SS interactions between TTF stacks, which is in sharp contrast to that in (TTF)(TCNQ). Structural analysis and theoretical studies afford a partial charge-transfer (ρ ≈ 0.52), leading to a system with the electronic structure close to quarter-filled. Resistivity measurements reveal that this material behaves as a metal down to 56 K and 22 K at 1 bar and 14.9 kbar, respectively. The thermopower is negative in the metallic regime, indicating the dominant role of the acceptor stacks for the observed conducting behavior. Analysis of single-crystal EPR spectra shows the remaining spin susceptibility at 4.3 K, suggesting the importance of the Hubbard U correction. These results highlight the judicious engineering of electronic and geometrical effects on the TTF core; the combined use of methyl and thiomethyl groups has decreased the TCNQ bandwidth while maintaining the segregated stacks, converting the metal to insulator (M-I) transition to more 4kF like. In addition, the enhanced SS contacts between the TTF stacks lead to more rapidly decreasing M-I transition temperature under various pressures.

Static Modulation Wave of Arrays of Halogen Interactions Transduced to a Hierarchy of Nanoscale Change Stimuli of Crystalline Rotors Dynamics.

Here we present a study where what can be seen as a static modulation wave encompassing four successive arrays of interacting iodine atoms in crystalline 1,4-Bis((4'-(iodoethynyl)phenyl) ethynyl)bicyclo[2,2,2]octane rotors changes the structure from one-half molecule to three-and-a-half molecules in the asymmetric unit below a phase transition at 105 K. The remarkable finding is that the total 1H spin-lattice relaxation rate, T1-1, of unprecedented complexity to date in molecular rotors, is the weighted sum of the relaxation rates of the four contributing rotors relaxation rates, each with distinguishable exchange frequencies reflecting Arrhenius parameters with different activation barriers ( Ea) and attempt frequencies (τo-1). This allows us to show in tandem with rotor-environment interaction energy calculations how the dynamics of molecular rotors are able to decode structural information from their surroundings with remarkable nanoscale precision.

Stable Metallic State of a Neutral-Radical Single-Component Conductor at Ambient Pressure.

Molecular metals have been essentially obtained with tetrathiafulvalene (TTF)-based precursors, either with multicomponent ionic materials or, in a few instances, with single-component systems. In that respect, gold bis(dithiolene) complexes, in their neutral radical state, provide a prototype platform toward such single-component conductors. Herein we report the first single-component molecular metal under ambient pressure derived from such Au complexes without any TTF backbone. This complex exhibits a conductivity of 750 S·cm-1 at 300 K up to 3800 S·cm-1 at 4 K. First-principles electronic structure calculations show that the striking stability of the metallic state finds its origin in sizable internal electron transfer from the SOMO-1 to the SOMO of the complex as well as in substantial interstack and interlayer interactions.

Conducting Anilate-Based Mixed-Valence Fe(II)Fe(III) Coordination Polymer: Small-Polaron Hopping Model for Oxalate-Type Fe(II)Fe(III) 2D Networks.

The mixed-valence FeIIFeIII 2D coordination polymer formulated as [TAG][FeIIFeIII(ClCNAn)3]·(solvate) 1 (TAG = tris(amino)-guanidinium, ClCNAn2- = chlorocyanoanilate dianionic ligand) crystallized in the polar trigonal space group P3. In the solid-state structure, determined both at 150 and at 10 K, anionic 2D honeycomb layers [FeIIFeIII(ClCNAn)3]- establish in the ab plane, with an intralayer metal-metal distance of 7.860 Å, alternating with cationic layers of TAG. The similar Fe-O distances suggest electron delocalization and an average oxidation state of +2.5 for each Fe center. The cation imposes its C3 symmetry to the structure and engages in intermolecular N-H···Cl hydrogen bonding with the ligand. Magnetic susceptibility characterization indicates magnetic ordering below 4 K and the presence of a hysteresis loop at 2 K with a coercive field of 60 Oe. Mössbauer measurements are in agreement with the existence of Fe(+2.5) ions at RT and statistic charge localization at 10 K. The compound shows semiconducting behavior with the in-plane conductivity of 2 × 10-3 S/cm, 3 orders of magnitude higher than the perpendicular one. A small-polaron hopping model has been applied to a series of oxalate-type FeIIFeIII 2D coordination polymers, providing a clear explanation on the much higher conductivity of the anilate-based systems than the oxalate ones.

Synthesis and Physical Properties of Purely Organic BEDT-TTF-Based Conductors Containing Hetero-/Homosubstituted Cl/CN-Anilate Derivatives.

Radical cation salts composed of a bis(ethylenedithio)tetrathiafulvalene (ET) donor with homo-/heterosubstituted Cl/CN anilic acids as purely organic molecular conducting materials formulated as [BEDT-TTF]2[HClCNAn] (1) and [BEDT-TTF][HCl2An] (2) have been prepared by electrocrystallization. Compounds 1 and 2 crystallized in the monoclinic space group P2/c for 1 and I2/a for 2, showing segregated donor-anion layers arranged in a α'-type donor packing pattern (1) and twisted parallel columns (2), respectively. Single-crystal conductivity measurements show that 1 is a semiconductor with room-temperature conductivity of 10-2 S cm-1 and an activation energy Ea of 1900 K.

Nanotexturing To Enhance Photoluminescent Response of Atomically Thin Indium Selenide with Highly Tunable Band Gap.

Manipulating properties of matter at the nanoscale is the essence of nanotechnology, which has enabled the realization of quantum dots, nanotubes, metamaterials, and two-dimensional materials with tailored electronic and optical properties. Two-dimensional semiconductors have revealed promising perspectives in nanotechnology. However, the tunability of their physical properties is challenging for semiconductors studied until now. Here we show the ability of morphological manipulation strategies, such as nanotexturing or, at the limit, important surface roughness, to enhance light absorption and the luminescent response of atomically thin indium selenide nanosheets. Besides, quantum-size confinement effects make this two-dimensional semiconductor to exhibit one of the largest band gap tunability ranges observed in a two-dimensional semiconductor: from infrared, in bulk material, to visible wavelengths, at the single layer. These results are relevant for the design of new optoelectronic devices, including heterostructures of two-dimensional materials with optimized band gap functionalities and in-plane heterojunctions with minimal junction defect density.

Localization versus Delocalization in Chiral Single Component Conductors of Gold Bis(dithiolene) Complexes.

The first examples of chiral single component conductors are reported. Both (S,S) and (R,R) enantiomers of 5,6-dimethyl-5,6-dihydro-1,4-dithiin-2,3-dithiolate (dm-dddt) ligand have been used to prepare anionic metal bis(dithiolene) complexes formulated as ([(n-Bu)4N][M(dm-dddt)2] (M = Au, Ni), which are isostructural according to single crystal X-ray analysis. Single crystal transport measurements indicate semiconducting behavior for the anionic radical Ni complexes, with low room temperature conductivity values and high activation energies. Electrocrystallization experiments provided neutral [M(dm-dddt)2] (M = Au, Ni) complexes. The neutral radical gold compounds show intermolecular S···S interactions in the solid state giving rise to layers interconnected through weak C-H···S hydrogen bonds. The most peculiar structural feature concerns a dissymmetry between the two dithiolene moieties, while the nickel counterpart is symmetric. Single crystal resistivity measurements show thermally activated behavior for the open-shell gold complexes, with room temperature conductivity values of 0.02-0.04 S·cm(-1) and activation energies strongly influenced by hydrostatic pressure. A thorough theoretical study on nickel anion radical and gold neutral radical bis(dithiolene) complexes applied to the chiral complexes [M(dm-dddt)2] (M = Au, Ni(-)) and to a series of previously reported compounds addressed the issue of symmetry versus asymmetry from an electronic coupling perspective between the two dithiolene ligands. It results that neutral gold complexes with dithiolene ligands without extended delocalization are Class II mixed-valent compounds in the Robin and Day classification, presenting an inherent tendency toward asymmetric structures, which can be however modulated by the intermolecular organization in the solid state.

Polymorphism and Superconductivity in Bilayer Molecular Metals (CNB-EDT-TTF)4I3.

Electrocrystallization from solutions of the dissymmetrical ET derivative cyanobenzene-ethylenedithio-tetrathiafulvalene (CNB-EDT-TTF) in the presence of triiodide I3- affords two different polymorphs (ß″ and κ) with the composition (CNB-EDT-TTF)4I3, both with a bilayer structure of the donors. These polymorphs differ in the packing patterns (ß″- and κ-type) of the donor molecules in each layer, in both cases with bifurcated C-N···H interactions effectively coupling head-to-head donor molecules between layer pairs. Two ß″ polymorphs can be obtained with different degrees of anionic ordering. In one disordered phase, ß″d, with a smaller unit cell, the triiodide anions are disordered over two possible positions in a channel between the donor bilayers, while in the ordered phase, ß″o, the triiodide anions occupy only one of those positions in this channel, leading to the doubling of the unit cell in the layer plane. These results for ß″ phases contrast with the κ polymorph previously reported, for which weaker disorder of the triiodide anions, over two possible orientations with 94 and 6% occupation factors, was observed. While the ß″ polymorphs remains metallic down to 1.5 K with a ρ300K/ρ4K resistivity ratio of 250, the κ polymorph presents a much smaller resistivity ratio in the range of 4-10 and superconductivity with an onset temperature of 3.5 K.